The planarity of five-membered rings is derived from a competition between ring-angle strain and stability of the torsional angles. The planar form maximizes the already stressed, smaller-than-normal, C-C bond angles, while puckering reduces the unfavorable eclipsed interactions. The structure, dynamics, and planarity of three anhydrides, succinic, methylsuccinic, and methylene (itaconic) anhydride, were studied and compared using chirped-pulse Fourier transform microwave spectroscopy.